Insecticidal composition comprising 1-p-chlorophenyl-2-nitro-1-tolylpropane



' secticides possess both properties in varying de- J Patented Jan.16,3951 '7 $553; PATENT orrics v I NSECTIGIDAL COMPOSITION. COMPRISINGl-p-CHLOROPHENYL- 2 -NITRO- 1 -TOLYL- PROEANE Henry B. Hass, WestLafayette, Ind., and Mayhard B. Neh'er', Athens, Ohio, assignors toPurdue'Res'earch Foundation, La Fayette, Ind., a

corporation of Indiana o Nol rawing. Application February 19, 1948;serial No.; 9,632

5 Claims, (Cl:1673.0)1 f f "Our invention relates toinsecticidal-composi- 'no entirely satisfactory killing" agent.- Aslwill tigns and is' -aparticularly concerned with matebe shown below,1-p-chlorophenyl-2-nitrol-p f alsfadaptedjior combatin flies; theMexican 'tolylp'ropane is highly effective against this :im bean beetle,and other common insect pests. eortaot pest at very low concentrationsand with More particularly, it relates 'to'theuse-"ofh-p s substantiallyno harm to the host, thus making -chlorophenyl-z-nitro-l-p-tolylpropane'as ah-"acour discovery unusually important from the tive ingredient insuch compositions,- and to point of 'v 'o p a l u ty. In a t methods ofproducing 1-p-chlorophenyl-2 nitrowhen used against house flies, itpossesses knockl-p-tolylpropane. down properties comparable with thoseof the lvlany iriaterials'aiid classes of materials "h e aliphaticthiocyanate known as Lethane, comein the past been recommended asinsecticides, monly accepted at the present time as a standardfungicides, pesticides, andthe like. The great Co erc o tj najority ofthese, however, havebeen irnprac- The 1 p-cholorophenyl-2-nitrol-p-tolylprotical for various reasons includingavailability, pane of ourinvention may be prepared as 1501'- cost. impractical physicalcharacteristics such lows: Six hundred and fifty milliliters of 85% asodor, undesirable l efiects on the pest host or ulfuric acid was cooledin an ice bathand then other object with which the product, comes in 260g. oftoluene added thereto. The resulting Co act, difiicnlty and. dangerof application, mixture was stirred until the temperature ie'tc. Ofequal, if not greater importance is the dropped below 10 C. and then g.of1-p-chlo high degree -of selectivity possessed by many 20iophenyl-2-nitro-lpropanol added at such a products of this character.For example, a

p l r agent may. be especially effective a against one or two mseotsbuthave no harmful ice bath w s removed nd irrin n in at action whatsoeveron any other wherf'app'lied room temperature for four or'five hours; Therepractieal quantities. Also, particular inse t suiting mixture was'thenpoured over cracked'ic'e are" found to be resistant to almost every kindof and extracted with ether. The eth fi ayeir insecticidal compound ofpractical utility known. was 5 then removed in "a" separatory tun l,Even closely relatedchemical compounds" often treated'with solid sodiumbicarbonate-to remove have Widely diiierent; effects upon bothpests'afid sulfuric acid. that might be in suspensiom -and their hosts,with the. result that a new material then evaporated on a steam plate.The resulting or type of'x'n'aterial" must be tested'under condisolidresidue was then'crystallized to give the tions simulating-those ofactual use before its ir '1 pr ph nyI-2 i r -1-po1y1nroutility can bedetermined. pane, having" a melting point of 95-'6 C. TI-{he Theerficacy of an insecticidal composition crude product may be"satisfactorily recrystalagainst housejfiies is usually measured in termslized'frorn absolute ethanol. The yield of the-def of its knock-down .orper, cent kill. some insired product obtained by .the procedure outlinedabove was 48%. ,j "'grees and hence the use'to be made of a given The'l-p-chlorophenyl-2-nitro-l-propanol used material should be known inorder to permit the in the above condensation operation was obtainedselection of the proper material or combination 40 by condensingp-chlorobenzaldehyde with nitro- -of materials. For example, pyrethrumhas the "ethane." A convenient method of eiiecting this "property ofproducing a high degree of knockcondensation .is."as' follows: Fourmoles of p-- down, but many ofthe insects immobilizedultichlorobenzaldehyde (562 gr) was stirred withfa inately recover.Other materials; such as di- "solution'ofl lflg. of sodium bisulfite in2000-m1. chloi odiphenyltrichloroethane, commonly noted of distilledwater until the exothermic formaas D. D. have high percentkill but arerelation of the sodium bisulfite addition complex was tively low inknock-down'andhence, their accomplete, as shown by a drop intemperature. tion is: not so quickly. seen. For the latter reason;This'took about 8 hours. The solution was cooled it is sometimes founddesirable. to combinefanf Tito room temperature by use of an ice bath.To agent-with a high percent kill with another hav-- *sothi's' was thenadded a solution prepared by re- '"inghighknock-down.'--------- acting330 g. (4.4 moles) of nitroethane with 180 jij We have on discovered acompound-namely,- 'g. (pf-sodium hydroxide in 800 ml. of Water at suchl-p-chlQij phehyl- Z 1- nitro' '-"1' p '-"to lylpropane', a rate thatthe temperature did not rise above 20 j which possesses theproperty ofhigh percent kill I C. The resulting mixture was stirred for one hour l''for certainftypes of insects. e. g., the. common and allowed to standovernight. The resulting housefly, and more important still; thelvlexican. x -mean-beet1e--for which-there haspreviously..beenmmiledthoa 'slurry of the sodium bisulfite-pechlorolow10 C. After the'addition wasrcomplete the rate that the temperature wasmaintained benitro'alcohol settled to the bottom of the flask?benzaldehyde complex. The solid material was removed by suctionfiltration and the organic material dissolved in ether and extractedseveral times with saturated sodium bisulfite solution to remove theunreacted p-chlorobenzaldehyde. The other solution was dried withanhydrous sodium sulfate and the ether evaporated' The conversion of1-p-chlorophenyl-Z-nitro-1-propanol was 4.90 g., or 55%. After removalof the latter, the resulting 1-p-chlorophenyl-2-nitro-1- propanol may befurther purified by distillation if desired.

The concentration of the sulfuric acid used in the above example may bevaried from about 85 to about 95% with satisfactory results. Similarly,the condensation temperature may be allowed to rise to about 40 C.without materially reducing the yield of the desired product.

" The exact quantity of l-p-chlorophenyl-2-ni- -tro-1-p-tolylpropaneutilized in insecticidal compositions will be found to vary ratherwidely and to a certain extent depends upon the particular .type ofcomposition in which the material is being employed, the method ofapplication, the nature .of the insect pest to be controlled, and otherfactors commonly encountered in the insecticidal art. Since the materialis relatively insoluble in some of the common solvents, this factor mustf a'lso naturally be taken into consideration. As

will be shown below, solubility in some instances may be increased byusing a mixture of solvents in place of a single solvent. Generallyspeaking, however, concentrations ranging from about 0.5 to 2.0%, basedupon the total weight of the fin- .ishe'd insecticidal composition, givesatisfactory results in fly spray compositions. When incorporated in asolid carrier such as Pyrax, a ground pyrophyllite or ground aluminumsilicate, concentrations ranging from 0.15 to 5.0 and even higherpercentages may be employed.

As liquid vehicles or carriers we may employ "Ultrasene, or other likepure petroleum distillates or even commercial kerosene where odor is not.too important a factor, or coal tar hydrocarbons such as xylene ortoluene. At 0.5% concentration l-p-chlorophenyl 2 nitro-l-p-tolyl--propane is completely soluble in Ultrasene but La 1.0% concentrationappears to be about the limit of its solubility in this particularsolvent. -However, by substituting 10% of n-butyl phthal- 'ate aconcentration of 1.0%, or better, can be 'readily obtained and bysubstituting 10% of butyl carbito-l for an equivalent amount of theUltrasene the concentration of l-p-chlorophenyl-Z-nitro-l-p-tolylpropane can be increased to 2.0%. Other combinations mayalso be satisfactorily employed. As a solid vehicle we may employ any ofthe various forms of ground aluminium silicate commonly employed ininsecticidal compositions, bentonite, fullers earth, kieselguhr, kao-"lin, talc, and the like.

' The effectiveness of 1-p-chlorophenyl-l-nitro- I l-p-tolylpropane as atoxic agent against female housefiies was determined as follows. Adultflies reared in the laboratory under constant conditions were introducedinto replicated spherical cages. Each cage was then placed on arevolving turntable and the flies subjected to an atom ized spraydelivered under constant pressure at the rate of 1.0 ml. per cage.Immediately after the flies in a cage were sprayed they were transferredto an observation cage in which they were maintained under constantconditions for twenty-four hours. At the end of that time the number ofdead flies was counted. The table which follows shows the resultsobtained by testing various solutions and concentrations in the mannergenerally described above. The average per cent kill shown below isbased upon several individual tests;

Table I leer Cent A o cenverage Gamer tration of Per Cent Toxicant 1007Ultrasene" 0.5 74.9 Ultrascne"- 1 0 88 6 rog, n-Ufilutyl phthalata 0trasene -1 10 Butyl carbitol The table given below gives the results ofa series of experiments carried out to compare the knock-down propertiesof l-p-chlorophenyl-Z-nitro-lp-tolylpropane, and various combinationsthereof, with Lethane, a commonly used knockdown agent in insecticidalcompositions. In this instance, however, the test insects, femalehouseflies, were subjected to the action of uniform amounts of spray ofdifferent compositions and concentrations and the times observed whenall of the flies in a given test had been knockeddown.

Table II M'lime i1; inutes or Composition 100% Knockdown 5% Lethane inUltrasene" 3 0.5% 1-p-Chlorophcnyl-2-nitro-l-p-Tolylpropan n Ultrasene7% 1.0% l-p-0hlorophenyl-2-nitro-l-p-T0Iylpropanc in Ultrasenc 3%complete mothproofing. The cloth remained normal in appearance.

In view of the data shown above, it can be seen that1-p-ch1oropheny1-2-nitro-l-p-tolylpropane possesses marked insecticidalactivity. Also it may be utilized in conjunction with materials such aspyrethrum, rotenone, derris extract, nicotine, organic thiocyanates, andthe like.

The insecticidal composition of our invention may be applied in a numberof different ways. For example, it may be dissolved in kerosene orsimilar petroleum distillates with or without the addition of othertoxicants and sprays. For use on plants, it may be dissolved in variousplant spraying oils and emulsified in water to produce sprayableemulsions. Any of the common emulsifying agents utilized for suchpurposes can be employed in conjunction with these insecticidalcompositions.

Now having described our invention, what we claim is:

1. An insecticidal composition containing, as

.p-chlorophenyl-2-nitro-1-to1ylpropane 6 V the active insecticidalcomponent thereof, 1-pchlorophenyl-2-nitro-1-tolylpropane.

2. An insecticidal composition containing, as the active insecticidalcomponent thereof, from about 0.15 to 5 per cent by weight ofl-p-chlorophenyl-2-nitro-1-tolylpropane.

3. The composition of claim 2 wherein the 1- is dispersed in a liquidpetroleum distillate as a carrier.

4. The composition of claim 2 wherein the 1- p-chloropheny1-2-nitrol-tolylpropane is dispersed in a liquid coal tar hydrocarbon as a carmen5. The composition of claim 2 wherein the composition contains a groundaluminum silicate as a carrier.

HENRY B. HASS. MAYNARD B. NEHER.

REFERENCES CITED Name Date Muller Apr. 2, 1946 Number i 1 Patent No.2,538,687

Certificate of Correction January 16 a HENRY B. HASS ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 3, line 62, for 1-nitroread 2-m'tr0- and that the said LettersPatent should be read as corrected above, so that the same may conformto the record of the case in the Patent Oflice.

Signed and sealed this 10th day of April, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent N 0. 2,538,687

HENRY B. HASS ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 3, line 62, for 1-nitroread .Q-nz'trm and that the said LettersPatent should be read as corrected above, so that the same may conformto the record of the case in the Patent Oflice.

Signed and sealed this 10th day of April, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

January 16,

1. AN INSECTICIDAL COMPOSITION CONTAINING, AS THE ACTIVE INSECTICIDALCOMPONENT THEREOF, 1-PCHLOROPHENYL-2-NITRO-TOLYLPROPANE.